Laser vaporized xCr/Al2O3 nanopowders with the particle size of ca. 15 nm were studied by XRF, EDX, HRTEM, XRD, DD, BET, TGA, UV–Vis DRS, Raman and PL spectroscopy methods as a catalytic system in dehydrogenation of isobutane. The nanopowders were found to contain not only the Cr6+ ions located on the surface of nanoparticles, but also two different types of Cr3+ sites as components of the γ-Al2O3 solid solution. One type consists of the bulk Cr3+b sites in a strong crystal field. Another type is represented by the Cr3+s sites residing near the surface of xCr/Al2O3 nanoparticles. Such sites are in a weak crystal field. It was shown that catalytic activity of the nanostructured xCr/Al2O3 system is provided by the high content of surface Cr3+s sites. The results obtained make it possible to propose the nanopowders obtained by laser synthesis as a promising catalytic system that can be used in the development of highly active catalysts for dehydrogenation of alkanes with the decreased chromium content.